Process for producing diesel oils



erties of such a mixture of fuels are unsatisable for use in Diesel engines. Those constitupmo Ma 21, 19.1 2,243,760

"uNlTlzb STATES PATENT OFFICE raocnss non rnlonucmo mnsnl. on.s

Friedrich Martin, Mulheim- Speldorf, Otto Roelen, -berhausen-Holten, and Paul Schalier, Oberhausen- Sterkrade, Germany, assignors to Ruhrchemie Aktlengeseilschait, Oberhausen- Holten, Germany No Drawing. Application March 4, 1937, Serial No. 129,088. In Germany March 4, was

9Claims. (01.44-9) P o the present no successful attempt has ordinary or slightly altered pressure which boil been made to replace the gas oils used iordrivat over 200 C. have proved particularly suiting Diesel engines, by distillation or extraction able for this purpose. v

products of carbonaceous substances such as pit- By the "use '01 the hydrocarbon oils obtained coal or brown-coal, as no one has succeeded in by the catalytic hydrogenation oi. carbon monproducing the ignition of such substances in a oxide it is possible, as with the tar oils before Diesel engine. Only in Diesel engines working referred to, to improve other hydrocarbons poor under particularly high compression is it posin hydrogen, such for example as the extraction sible to make use of the products or the-disproducts 01 pit coal and brown coal; products or tillation of brown coal or pit-coal tar. How- 10 a mild hydrogenation-and hydrocarbons that,

ever it has been proposed to mix tar oils, such as are solid under normal conditions can also be pit-coal tar oil with gas oil, but here again there treated in this manner.

has been no satisfactory result. 0n the one If these solid hydrocarbons are insoluble in hand the aspha-ltic and resinous constituents dissolved in the pit-coal tar' oil produce in the comthe eflect oi which is to dissolve the solid bodies bustion chamber of the Diesel engine deposits r or to distribute them in'a very fine state of dicarbon, and on the other hand the ignition propv s onhe rarafl n c oi s are added to the factory. The gas oil added favourably afl'ec'ts the resulting i re is o e wh h will r a ily the readiness of the mixtures to ignite to such ni e 1n he Di sel engine. The PI P which are suitable depend upon the nature of glue, but the delay in ignition peculiar to gas the substances used, and the best conditions unoil, when gas oil is used in admi ture with t der which the mixing is eflectedare in ever oils, is insumolent, so that the mixture injected c se de e i d by simple exper ment. into the Diesel-engines gives an extremely short Whereas hitherto for the burpose oi convertbummg period. The sharp increase 1' pressure ing any hydrogenation oil into a usable Diesel produced by the high speed of combust f oil it has been essential to increase by expensive the mixture is the cause 01' the considerable means t e y o en content to about 1 3%. knocking when such dlmoultly ignitable fuels are accordin o the present invention the simp e used in Diesel engines. mixing gether of the hydrocarbon oils rich in It is known that those middle and heavy oil hydrogen and a hy rogena ion P od c wi h a boiling t temperatures lying between 200 0 considerably smaller content of hydrogen pro!- C. which are obtained by the catalytic convertimes a very good usable Diesel oil. The possision 1 carbon m xi and hydrogen into ynbility of avoiding large additions of hydrogen is th tic hydrocarbons, are ujtable for use in Diesel or very great practical importance because it is engines. These oils excel by reason of their precise]? the addition 1 y ogeninlarge q anreadiness to ignite, and in their behaviour. in tit1e$that is to o the carrying out of 0011- th engine cylinder resemble very closely t siderable hydrogenation-that necessitates the gas oils used up to the present in Diesel engines. It would therefore be logical to assume that the quires high Pressures or considerable. l es of use in Diesel engines of mixtures of tar oils and 38590115 mustimentswhen using h Products the synthetic oil hereinbefore referred to would P9 in hydrogen which are herein-before referred o s m some ungatisfactgry wm to, it is necessary however to ensure that the It has been found that'the tar oils, such as content of hydrogen is t least so high that the pit-coal tar oils, brown coal tar 0118'. low tem- 45 added hydrocarbimofls rich 'in hydrogen $11011 perature distillation tars, shale oils, wood tar as are obtained by the catalytic hydrogenation and the like, which are obtained during the high of carbon monoxide, do not cause excessive quanor low temperature coking or carbonaceous bitines hydrombons be Separated out s a tuminous substances such as pit-coal,.-brown coal, flocculent precipitate from the products poor in shale, wood, peat and the like, are so improved 5 h e Occasionally it has p oved to be adby the addition or synthetic oil that by such vantageous torreoipitate from the products i 0! addition to them a fuel i produced th t is tin hydrogen the substances which are capable oi precipitation by means of the hydrocarbons ents of paraffin hydrocarbons obtained'by the rich in hydrogen, wi h a mal quantity 1 ancatalytic hydrogenation of ca bo'n monoxide at o er yd o on i i hyd o n. such as gas the paraiilnic oils. dissolving agents are also used,

products poor in hydrogen in such quantity that use or particular agents such as catalysts, or reiiication point. Whereas oil. The products from which the precipitated substances have been removed by filtration give an extremely good Diesel oil when mixed with the hydrocarbon oils richin hydrogen produced from a mixture of carbon monoxide and hydrogen. By this means substances such as extracts from coal to which only a little hydrogen has been addedcan be employed in a very useful manner. The insoluble constituents obtained by content of hydrogen and which have been separated out from the insoluble substances are first with fullers earth. After filtration 170 parts by weight of a clear unvarying Diesel oil having a specific gravity of 0.85 is obtained. This Diesel oil ignites very readily and has an excellent solidification point, which lies at C. Example 2.70 parts'of brown coal tar. boiling at temperatures lying between 200 and 300 C. whose specific gravity is 0.907 and which has a solidification point of 23.5 C., are mixed with parts by weight of a paraflin oil obtained from carbon monoxide and hydrogen whose specific gravity is 0.77 and which at temper- T atures lying between 200 and 310 C. After the removal of thevconstituents "separated out, a 1 Diesel oil is obtained which has a specific gravity, .of 0.866 and asolidification point of 16.5 C.

' This oil was found to be very satisfactory when subjected to a further weak hydrogenation before they are mixed with the products rich in hydrogen. Hydrogenation can be carried out under particularly simple reaction conditions.

It is of particular advantage to the present processthat when the two components are mixed together there is not only an improvement in the 'quality of the mixture for engines but also a refining of the components-poorer in hydrogen. Thus it is already known that the added synthetic paraflin hydrocarbons separate out from the hydrocarbons poor in hydrogen the constituents which in the Diesel engine lead to the deposition of carbon. The separated substances may be very simply removed from the mixture of oils, the refining agent, namely the synthetic parafiin hydrocarbons, preferably remaining in the hydrocarbons poor in hydrogen, to be burnt in the Dieselengine. Thus the addition of these synthetic parafiln hydrocarbons renders possible the use of the crude tar oils directly instead of being obliged to commence with the much more .expensive distillation products.

The mixture of oils together with the sub-'- stancesseparated out may be treated first with lye and then with fullers earth or alternatively it may be treated with fullers earth alone.

By mixing an oil whose specific gravity is near to '1, with a synthetic hydrocarbon oil which has a specific gravity of approximately 0.75, a mixture is obtained which has aspeciiic gravity of about 0.84 to 0.86 just as have the Diesel oils hitherto used. r

' It is desirable tofavourably influence the solidvery low solidification point and the synthetic parafiin hydrocarbons employed according to the process of the invention-have a high solidlfication point, the Diesel oil produced by mixing together the two components has a solidification point, normal for Diesel oils, of for example -20 C. A

The process is hereinafter explained by means of examples.'

" Example 1.75 parts by weight of crude heat-- ing oil obtained from'pit-coal tarand having a specific gravity of 1.09, which oil will not ignite in a Diesel engine, are intimately mixed at ordinary temperature with 100 parts by weight of a parafiln oil of a specific gravity of 0.76, an initial boiling point of about 200 C.', and a solidification point of 20 .0. obtained from carbon monoxide and hydrogen. on admixture black insoluble substances and liquid impurities are removed from thepit-coal tar oil. The mixture of oils is treated at a slightly raised temperature first with a 30% solution of caustic soda and then the taroils have a.

testedin'aD'iesel engine.

Example 3.-65 parts oi a pit-coal distillate boiling at temperatures lying between 215 and 360 C., having a specific gravity of 1.07 and a solidification point of 29" C., are mixed with 35 parts of the same synthetic oil as used in Example 2. After the removal of the constit-" after treatment of the uents separated out and mixture of oils with caustic soda and.fullers earth, a Diesel 011 is obtained which has a specific gravity of 0.96 and a solidification point of 18" C. and which ignites very readily.

Example 4.-65 parts of a fraction, boiling at between.200 and 320 C. of a tar obtained from pit-coal by low temperature distillation and which has a specific gravity of 0.991 and a solidification with 35 parts of the point of 27.5 C. is mixed same synthetic oil as used in Example 2. After the removal of the constituents separated out by treatment of the mixture of oils with fullers earth, a Diesel oil is obtained which-has a specific gravity of 0.912 and a solidification point of -'-20.5' C.

Example 5.- parts of between 200 and 320 C. of 'a dephenolatedtarobtained from pit-coal tillation, which fraction 0.968 and a solidification pointlying below 50" C. are mixed with 30 parts of the same synthetic hydrocarbon as used in Example2. After the constituents separated out have been removed. a Diesel oil is obtained which of 0.707 and a solidification point of 23 C. 1

Example 6.-70 parts of a hydrogenation oil obtained from brown coal in the first hydrogenabeen only incompletely tion stage. having th hydrogenated, whose solidification point is 17.5"

C. having a specific gravity of 0.901 and a boilin ismixedwith 30partsof range of 200 to320 C. the same synthetic oil as in Example 1. After the removal of .the separated :oi! constitucuts by treatment-of the mixture of oils pit-coal in the first hydrogenation stage,- and which has a boiling range of from 200 to 320 C.',

' a specific gravity of 0.974 and a solidification point lyingbelo'w 40" C. was used as the component poor in hydrogen. The content of acidic constituents of this hydrogenation oil which had been incompletely saturated with hydrogen,

amounted to 16.0%. 60 parts of this hydrogenation oil were mixed with 40 parts of the same a fraction, boiling at by low temperature dlshas a specific gravity of has a specific gravity with I fullers earth, a Diesel 011 is obtained whose specife ic gravity is 0.861 'and synthetic oil as used in Example 2. After the removal oi the separated-oi! constituents a Diesel oil was obtained having a specific gravity of 0.805 and a solidification point oi 20 C. This mixture likewise can be stored without deterioration.

Example 8.-'70 parts of a liquefied extract oi pit-coal which has been obtained by mild hydrogenation and which boils at between 200 and ammo 4. A iuel ior driving Diesel motors, oi parallinic oils rich in hydrogen obtained by the catalytic hydrogenation oi carbon monoxide and having boiling points ranging from 200' O. to 320 C. and of tar oils obtained by the dis-" tlllation oi carbonaceous materials in simple admixture 320 C. while having a specific gravity oi 1.028

and a solidification point oi .43'.5 0., are mixed with 30 parts oi the same synthetic oil as usedin Example2. when the constituents separatedofi. are removed a Diesel oil is obtained which has a specific gravity of 0.946 and a solidification point of -22.5 C.

Example 9.80 litres of a heavy anthracene 5. A Inc] for driving Diesel motors, consisting of paraiiinic oils rich in hydrogen obtained by the catalytic hydrogenation oi. carbon monoxide and having boiling points ranging irom 200 C. to

320 C. and of extraction products from carbo oil are mixed at ordinary temperature with 1. A fuel for driving Diesel motors, consisting of paraifinic oils obtained by the catalytic reduction of carbon monoxide to hydrocarbons and having boiling points ranging from 200' C. to 320 C. and of carbonaceous products poor in hydrogen in simple admixture.

2. A fuel for driving Diesel motors, consisting of parafilnic oils rich in hydrogen obtained by the catalytic hydrogenation at carbon monoxide having boiling points ransing from 200' C. to 320' 0., and of liquid carbonaceous products poor in hydrogen in simple admixture. v

3. A fuel for driving Diesel motors, consisting of paramnic oils rich in hydrogen obtained by the catalytic hydrogenation of carbon monoxide and having boiling. points ranging Irom 200 C. to 320 C. and of solid carbonaceous products poor in hydrogen in simple admixture.

aceous materials in simple admixture.

8. A fuel for driving. Diesel motors, consisting oi paraifinic oils rich in hydrogen obtained by the catalytic hydrogenation of carbon mon-' oxide and having boiling points ranging from 200 C. to 320 0. mixed with hydrogenation products 'oi.carbonaceous materials oi nature diliering from and poorer in hydrogen than the paraillnicoils. r

7. A fuel for driving'Diesei motors, consisting oi parafiinic oils obtained by the catalytic reduction oi carbon monoxide to hydrocarbons and having boiling points ranging irom' 200 C.- to 320 C. and oi carbonaceous products poor in hydrogen, in such proportions that the mixture 1 has the same specificgravity as ordinary Diesel oils.

s. a fuel according to claim '1, imdriving Diesel motors, which contains. in addition, solvents for the carbonaceous substances that are poor in hydrogen and are insoluble in the parafiinlc oils rich in hydrogen. 9. A fuel for driving Diesel motors, according to'ciaim 6, wherein the hydrogenated products oi carbonaceous materials are obtained by hydroaenation of the said materials to such an extent that noappreciable quantities oi hydrocarbons fioccuiate on admixture with the paraifinic oils rich in'hydrogen.

FRIEDRICH MIAR'I'IN.

PAUL BCHALLER.

consisting 

